TWI480358B - Organic electroluminescence element - Google Patents

Description

Organic electric field light-emitting element

The present invention relates to an organic electric field light-emitting element (hereinafter sometimes referred to as "organic electroluminescence element" or "organic EL element").

The organic EL element has characteristics such as self-luminous and high-speed response, and the industry expects to apply it to a flat panel display. In particular, since a two-layer type (stacked type) light-emitting element in which a hole transporting organic thin film (hole transport layer) and an electron transporting organic thin film (electron transport layer) are laminated is proposed, it is 10 V or less. The low-voltage illuminating large-area light-emitting elements are of interest. The basic structure of the laminated organic EL element is a positive electrode/hole transport layer/light emitting layer/electron transport layer/negative electrode, wherein the light emitting layer can function as a light emitting layer or an electron transport layer together with the light emitting layer as in the above two layer type. .

In order to simultaneously achieve low voltage and high luminous efficiency, various studies have been conducted on such organic EL elements. As disclosed in Patent Document 1, a specific nitrogen-containing heterocyclic derivative is used as a high electron transporting material in the electron injecting layer and the electron transporting layer, thereby achieving low voltage and high efficiency. The driving voltage can be lowered by using the high electron transporting material of Patent Document 1, but the use of the phosphorescent material in the light emitting layer causes a problem that the luminous efficiency is lowered. The reason for this is that when the commonly used hole-transporting material is used as the main body, the phosphorescent material is mostly hole-transporting. If an electron-transporting material is used to inject too much electron into the light-emitting layer, electron flow in the light-emitting layer may occur. Blocking, the carrier balance of the electron and the hole is destroyed, resulting in a decrease in luminous efficiency.

As described above, Patent Document 1 discloses an experimental example using a fluorescent light-emitting device, but does not disclose an experimental example using a phosphorescent light-emitting material, and does not indicate a problem of a decrease in luminous efficiency when a phosphorescent light-emitting material is used, and the like, and currently uses a phosphorescent light-emitting material. The technology required at the time is not disclosed or suggested.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-217547

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electric field light-emitting element which can reduce a driving voltage while maintaining high luminous efficiency.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, it has been found that a combination of a phosphorescent material having high electron transport properties and a high electron transporting material can promote electron flow in the light emitting layer and improve the carrying of holes and electrons. The sub-equilibrium can simultaneously achieve low voltage and high luminous efficiency, especially when a phosphorescent material using a tetradentate ligand platinum complex is used, high luminous efficiency and low driving voltage can be achieved.

The present invention has been made based on the above findings of the inventors of the present invention, and means for solving the above problems are as follows. which is,

<1> An organic electroluminescent device comprising at least one organic layer containing a light-emitting layer between an anode and a cathode, wherein at least one layer contains at least one selected from the group consisting of nitrogen-containing heterocyclic derivatives represented by the formula (1), and At least one layer contains an electron-transporting phosphorescent material represented by the general formula (2);

Wherein, in the general formula (1), A1 to A3 are each independently a nitrogen or a carbon atom; Ar ¹ is a substituted or unsubstituted core carbon number of 6 to 60 aryl groups, or a substituted or unsubstituted core carbon number of 3 to 60 heteroaryl groups; a group, Ar ² is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, a substituted or unsubstituted carbon number 1 to 20 alkyl group, Or a substituted or unsubstituted C 1-20 alkoxy group; but one of Ar ¹ and Ar ² is a substituted or unsubstituted core carbon number 10 to 60 condensed ring group, or a substituted or unsubstituted core carbon number 3 to 60 monoheterofused ring groups; L ¹ and L ^{2 are} each independently a single bond, substituted or unsubstituted core carbon number 6 to 60 extended aryl, substituted or unsubstituted core carbon number 3 to 60 heteroaryl group , or a substituted or unsubstituted hydrazine group; R is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, substituted or unsubstituted a carbon number of 1 to 20 alkyl groups, or a substituted or unsubstituted carbon number of 1 to 20 alkoxy groups; n is an integer of 0 to 5, and when n is 2 or more, a plurality of Rs may be the same or different, and adjacent Multiple R groups can be bonded to each other Into a carbocyclic aliphatic ring or a carbocyclic aromatic ring;

In the general formula (2), X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or a nitrogen atom; and one or more of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom; X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each independently represent a carbon or nitrogen atom; X ¹¹ and X ¹² each independently represent a carbon or nitrogen atom, and X ¹³ , X ¹⁴ and X ¹⁵ each independently represent carbon, nitrogen, oxygen or sulfur. The atom, the 5-membered ring skeleton represented by X ¹¹ , X ¹² , X ¹³ , X ¹⁴ and X ¹⁵ contains 2 or less nitrogen atoms; and L represents a single bond or a divalent linking group.

<2> The organic electroluminescent device of <1>, wherein the nitrogen-containing heterocyclic derivative represented by the formula (1) is represented by the formula (3),

Wherein, A ¹ to A ^{3 are} each independently a nitrogen or a carbon atom; Ar ¹ is a substituted or unsubstituted core carbon number 6 to 60 aryl group, or a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group; Ar ² a hydrogen atom, a substituted or unsubstituted core having 6 to 60 aryl groups, a substituted or unsubstituted core having 3 to 60 heteroaryl groups, a substituted or unsubstituted C 1-20 alkyl group, or a substituted or unsubstituted The substituted carbon number is 1 to 20 alkoxy; but one of Ar ¹ and Ar ² is a substituted or unsubstituted core carbon number 10 to 60 condensed ring group, or a substituted or unsubstituted core carbon number of 3 to 60 mono a condensed cyclic group; each of L ¹ and L ^{2 is} independently a single bond, a substituted or unsubstituted core having 6 to 60 aryl groups, a substituted or unsubstituted core having 3 to 60 carbon atoms, or a substituted or unsubstituted Substituted exocyclic group; R' is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, a substituted or unsubstituted carbon number 1~ 20 alkyl, or substituted or unsubstituted C 1-20 alkoxy.

<3> The organic electroluminescent device according to <2>, wherein the nitrogen-containing heterocyclic derivative represented by the formula (3) is represented by the formula (4).

Wherein, A ¹ and A ² are each independently a nitrogen or a carbon atom; Ar ¹ is a substituted or unsubstituted core carbon number 6 to 60 aryl group, or a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group; Ar ² a hydrogen atom, a substituted or unsubstituted core carbon number of 6 to 60 aryl, a substituted or unsubstituted core carbon number of 3 to 60 heteroaryl, a substituted or unsubstituted carbon number of 1 to 20, or a substituted or unsubstituted The carbon number is 1 to 20 alkoxy; but one of Ar ¹ and Ar ² is a substituted or unsubstituted core carbon number 10 to 60 condensed ring group, or a substituted or unsubstituted core carbon number of 3 to 60 single a condensed cyclic group; each of L ¹ and L ^{2 is} independently a single bond, a substituted or unsubstituted core having 6 to 60 aryl groups, a substituted or unsubstituted core having 3 to 60 carbon atoms, or a substituted or unsubstituted Substituted exocyclic group; R' and R" are each independently a hydrogen atom, a substituted or unsubstituted core carbon number of 6 to 60 aryl, a substituted or unsubstituted core carbon number of 3 to 60 heteroaryl, substituted or unsubstituted The carbon number is 1 to 20 alkyl groups, or the substituted or unsubstituted carbon number is 1 to 20 alkoxy groups; and R' and R" may be the same or different.

<4> The organic electroluminescence device of any one of <1> to <3>, wherein among the nitrogen-containing heterocyclic derivatives represented by at least one of the general formulae (1), (3) and (4), L At least one of ¹ and L ² is selected from a functional group represented by the following structural formula,

The organic electroluminescent device according to any one of <1> to <4> wherein the nitrogen-containing heterocyclic derivative represented by at least one of the general formulae (1), (3) and (4) In the above, Ar ¹ is a functional group represented by any one of the general formulae (5) to (14).

In the above formula, R ¹ to R ⁹² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 1-20 alkoxy group, a substituted or unsubstituted one. Core carbon number 6~40 aryloxy, substituted or unsubstituted core carbon number 12~80 diarylamine group, substituted or unsubstituted core carbon number 6~40 aryl, substituted or unsubstituted core carbon number 3 a ~40 heteroaryl group, or a substituted or unsubstituted core carbon number 18 to 120 diarylamino aryl group; L ³ represents a single bond or a substituent represented by the following structural formula,

The organic electroluminescent device of any one of <1> to <5>, wherein the compound represented by the formula (2) is represented by the formula (15),

In the general formula (15), X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or a nitrogen atom; and any one or more of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom; R ⁴¹ and R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are each independently a hydrogen atom or a substituent; X ¹¹ and X ¹² are each independently a carbon or a nitrogen atom, and X ¹³ , X ¹⁴ and X ¹⁵ are independently carbon, nitrogen and oxygen, respectively. Or a sulfur atom, the 5-membered ring skeleton represented by X ¹¹ , X ¹² , X ¹³ , X ¹⁴ and X ¹⁵ has a number of nitrogen atoms of 2 or less; an L form bond or a divalent linking group.

<7> The organic electroluminescent device according to <6>, wherein the compound represented by the formula (15) is represented by the formula (15a-1).

Wherein X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or a nitrogen atom; and any one of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom; R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent; X ⁵³ , X ⁵⁴ and X ⁵⁵ are each independently a carbon or a nitrogen atom; a nitrogen atom of a 5-membered ring skeleton containing X ⁵³ , X ⁵⁴ and X ⁵⁵ The number is 1 or 2; L represents a single bond or a divalent linking group.

<8> The organic electroluminescent device according to <7>, wherein the compound represented by the formula (15a-1) is represented by the formula (15a-2),

Wherein X ¹ , X ² , X ³ and X ^{4 are} each independently a carbon or a nitrogen atom; and any one of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom; R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently a hydrogen atom or a substituent; X ⁵³ and X ⁵⁴ each independently a carbon or nitrogen atom; a 5-membered ring skeleton containing X ⁵³ and X ^{54 has} a number of nitrogen atoms of 1 or 2; R ⁷⁵ represents a hydrogen atom or a substituent; an L form bond or a divalent linking group.

<9> The organic electroluminescent device according to <8>, wherein the compound represented by the formula (15a-2) is represented by the formula (15a-3),

X ¹ , X ² and X ^{4 in the} formula (15a-3) each independently represent a carbon or a nitrogen atom; and R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent; X ⁵³ and X ⁵⁴ each independently represent a carbon or nitrogen atom; the 5-membered ring skeleton containing X ⁵³ and X ^{54 has} a number of nitrogen atoms of 1 or 2; R ⁷⁵ represents a hydrogen atom or a substituent; and L represents a single bond or a divalent Linkage base.

<10> The organic electroluminescent device according to <6>, wherein the compound represented by the formula (15) is represented by the formula (15b-1).

In the formula (15b-1), X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or a nitrogen atom; and any one of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom; R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent; X ⁶¹ represents a carbon or a nitrogen atom, and X ¹³ , X ¹⁴ and X ¹⁵ each independently represent a carbon, nitrogen, oxygen or sulfur atom. The 5-membered ring skeleton represented by X ⁶¹ , carbon atom, X ¹³ , X ¹⁴ and X ¹⁵ has a number of nitrogen atoms of 2 or less; an L form bond or a divalent linking group.

<11> The organic electroluminescent device according to <10>, wherein the compound represented by the formula (15b-1) is represented by the formula (15b-2),

In the general formula (15b-2), X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or a nitrogen atom; and any one of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom; R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent; X ⁹⁴ and X ⁹⁵ each independently represent a carbon or a nitrogen atom; at least one of X ⁹⁴ and X ⁹⁵ represents a carbon atom; ⁹³ represents a hydrogen atom or a substituent; an L form bond or a divalent linking group.

<12> The organic electroluminescent device according to <11>, wherein the compound represented by the formula (15b-2) is represented by the formula (15b-3),

In the general formula (15b-3), X ¹ , X ² and X ⁴ each independently represent a carbon or a nitrogen atom; and any one of X ¹ , X ² and X ⁴ represents a nitrogen atom; R ⁴¹ , R ⁴² and R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent; X ⁹⁴ and X ⁹⁵ each independently represent a carbon or a nitrogen atom; at least one of X ⁹⁴ and X ⁹⁵ represents a carbon atom; and R ⁹³ represents a hydrogen atom or a substitution. A group; L represents a single bond or a divalent linking group.

The organic electroluminescent device according to any one of the above aspects, wherein the light-emitting layer contains a polydentate ligand metal complex having a partial structure represented by the general formula (2) and Tetradentate ligand platinum represented by formulas (15), (15a-1), (15a-2), (15a-3), (15b-1), (15b-2), and (15b-3) At least one of the objects.

The organic electroluminescent device according to any one of <1> to <13> wherein the light-emitting layer contains a polydentate ligand metal complex having a partial structure represented by the general formula (2) and a general formula Tetradentate ligand platinum complex represented by (15), (15a-1), (15a-2), (15a-3), (15b-1), (15b-2) and (15b-3) At least one of, and at least one body material.

<15> The organic electroluminescent device according to <14>, wherein at least one of the host materials has hole transport properties.

The organic electroluminescent device according to any one of <1> to <15> wherein the nitrogen-containing heterocyclic derivative is used as at least one of an electron injecting material and an electron transporting material.

<17> The organic electroluminescent device according to any one of <1> to <16> wherein the layer containing the nitrogen-containing heterocyclic derivative contains a reducing dopant.

<18> The organic electroluminescent device according to <17>, wherein the reducing dopant is selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, At least one of an alkaline earth metal halide, a rare earth metal oxide, a rare earth metal halide, an alkali metal organic complex, an alkaline earth metal organic complex, and an organic complex of a rare earth metal.

[Effects of the Invention]

The present invention can solve the prior problems, and can provide an organic electric field light-emitting element which can reduce the driving voltage while maintaining high luminous efficiency.

(organic electric field light-emitting element)

The organic electroluminescent device of the present invention has at least one organic layer containing a light-emitting layer between the anode and the cathode, wherein at least one layer contains at least one selected from a specific nitrogen-containing heterocyclic derivative, and at least one layer contains a specific electron Transmissive phosphorescent material.

<Nitrogen-containing heterocyclic derivative>

The nitrogen-containing heterocyclic derivative contains at least one selected from the group consisting of nitrogen-containing heterocyclic derivatives represented by the formula (1).

In the general formula (1), A ¹ to A ³ are each independently a nitrogen atom or a carbon atom. Ar ¹ is a substituted or unsubstituted core carbon number of 6 to 60 aryl groups, or a substituted or unsubstituted core carbon number of 3 to 60 heteroaryl groups. Ar ² is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, a substituted or unsubstituted carbon number 1 to 20 alkyl group, or a substitution Or an unsubstituted carbon number of 1 to 20 alkoxy groups. One of Ar ¹ and Ar ² is a substituted or unsubstituted core carbon number 10 to 60 fused ring group, or a substituted or unsubstituted core carbon number 3 to 60 monoheterofused ring group. L ¹ and L ² are each independently a single bond, a substituted or unsubstituted core carbon number 6 to 60 extended aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, or a substituted or unsubstituted hydrazine base. R is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, a substituted or unsubstituted carbon number 1 to 20 alkyl group, or a substitution or The unsubstituted carbon number is 1 to 20 alkoxy; n is an integer of 0 to 5. When n is 2 or more, a plurality of R may be the same or different, and a plurality of adjacent R groups may be bonded to each other to form Carbocyclic aliphatic ring or carbocyclic aromatic ring.

The nitrogen-containing heterocyclic derivative represented by the formula (1) is preferably represented by the formula (3).

In the general formula (3), A ¹ to A ³ are each independently a nitrogen atom or a carbon atom. Ar ¹ is a substituted or unsubstituted core carbon number 6 to 60 aryl group, or a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, Ar ² is a hydrogen atom, and the substituted or unsubstituted core carbon number is 6 to 60. The aryl group, substituted or unsubstituted core carbon number is 3 to 60 heteroaryl groups, substituted or unsubstituted carbon number 1 to 20 alkyl groups, or substituted or unsubstituted carbon number 1 to 20 alkoxy groups. One of Ar ¹ and Ar ² is a substituted or unsubstituted core carbon number 10 to 60 fused ring group, or a substituted or unsubstituted core carbon number 3 to 60 monoheterofused ring group.

L ¹ and L ² are each independently a single bond, a substituted or unsubstituted core carbon number 6 to 60 extended aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, or a substituted or unsubstituted hydrazine base.

R' is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, a substituted or unsubstituted carbon number 1 to 20 alkyl group, or a substitution Or an unsubstituted carbon number of 1 to 20 alkoxy groups.

The nitrogen-containing heterocyclic derivative represented by the formula (3) is preferably represented by the formula (4).

In the above formula (4), A ¹ and A ² are each independently a nitrogen or a carbon atom.

Ar ¹ is a substituted or unsubstituted core carbon number of 6 to 60 aryl groups, or a substituted or unsubstituted core carbon number of 3 to 60 heteroaryl groups. Ar ² is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, a substituted or unsubstituted carbon number 1 to 20 alkyl group, or a substitution Or an unsubstituted carbon number of 1 to 20 alkoxy groups. One of Ar ¹ and Ar ² is a substituted or unsubstituted core carbon number 10 to 60 fused ring group, or a substituted or unsubstituted core carbon number 3 to 60 monoheterofused ring group.

L ¹ and L ² are each independently a single bond, a substituted or unsubstituted core carbon number 6 to 60 extended aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, or a substituted or unsubstituted hydrazine base.

R' and R" are each independently a hydrogen atom, a substituted or unsubstituted core having 6 to 60 aryl groups, a substituted or unsubstituted core having 3 to 60 heteroaryl groups, and a substituted or unsubstituted carbon number of 1 to 20 An alkyl group, or a substituted or unsubstituted C 1-20 alkoxy group; R ^' and R" may be the same or different.

In the nitrogen-containing heterocyclic derivative represented by at least one of the general formulae (1), (3) and (4), at least one of L ¹ and L ² is preferably selected from the functional groups represented by the following structural formulas.

In the nitrogen-containing heterocyclic derivative represented by at least one of the general formulae (1), (3) and (4), Ar ¹ is preferably a functional group represented by any one of the general formulae (5) to (14). .

In the above formula, R ¹ to R ⁹² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 1-20 alkoxy group, a substituted or unsubstituted group. Core carbon number 6~40 aryloxy, substituted or unsubstituted core carbon number 12~80 diarylamine group, substituted or unsubstituted core carbon number 6~40 aryl, substituted or unsubstituted core carbon number 3 ~40 heteroaryl, or substituted or unsubstituted core carbon number 18-120 diarylaminoaryl. L ³ represents a single bond or a substituent represented by the following structural formula.

Specific examples of the nitrogen-containing heterocyclic derivative which can be used in the present invention are the following compounds, but are not limited thereto.

The above nitrogen-containing heterocyclic derivative is preferably used as at least one of an electron injecting material and an electron transporting material.

The nitrogen-containing heterocyclic derivative is contained in at least one layer of the organic layer, and is preferably contained in at least one of the electron injecting layer and the electron transporting layer.

The electron injecting layer and the electron transporting layer are membrane layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side.

The layer (organic layer, electron injecting layer, electron transporting layer) containing the above nitrogen-containing heterocyclic derivative preferably contains a reducing dopant.

The reducing dopant is preferably selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earths. At least one of a metal halide, an alkali metal organic complex, an alkaline earth metal organic complex, and an organic complex of a rare earth metal.

The amount of the above-mentioned reducing dopant to be used varies depending on the type of the material, and is preferably 0.1 to 99% by weight, more preferably 0.3 to 80% by weight, still more preferably 0.5 to 50% by weight based on the material of the electron transporting layer or the electron injecting layer.

The electron transport layer and the electron injecting layer may be formed by a known method, for example, by a vapor deposition method, a wet film formation method, an MBE (molecular beam epitaxy) method, a cluster ion beam method, or a molecular lamination method. The LB (Langmuir-Blodgett) method, the printing method, the transfer method, and the like are suitably formed.

The thickness of the above electron transport layer is preferably from 1 to 200 nm, more preferably from 1 to 100 nm, still more preferably from 1 to 50 nm.

The thickness of the electron injecting layer is preferably from 1 to 200 nm, more preferably from 1 to 100 nm, still more preferably from 1 to 50 nm.

<Electron transporting phosphorescent materials>

The electron-transporting phosphorescent material preferably contains an electron-transporting phosphorescent material represented by the formula (2).

In the general formula (2), X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or a nitrogen atom. Any one or more of the nitrogen atoms of X ¹ , X ² , X ³ and X ⁴ . X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each independently represent a carbon or nitrogen atom. X ¹¹ and X ¹² each independently represent a carbon or nitrogen atom, and X ¹³ , X ¹⁴ and X ¹⁵ each independently represent a carbon, nitrogen, oxygen or sulfur atom, represented by X ¹¹ , X ¹² , X ¹³ , X ¹⁴ and X ¹⁵ . The number of nitrogen atoms contained in the 5-membered ring skeleton is 2 or less. L represents a single bond or a divalent linking group.

The compound represented by the formula (2) is preferably represented by the formula (15).

In the general formula (15), X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or a nitrogen atom. Any one or more of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent. X ¹¹ and X ¹² each independently represent a carbon or nitrogen atom, and X ¹³ , X ¹⁴ and X ¹⁵ each independently represent a carbon, nitrogen, oxygen or sulfur atom, represented by X ¹¹ , X ¹² , X ¹³ , X ¹⁴ and X ¹⁵ . The number of nitrogen atoms contained in the 5-membered ring skeleton is 2 or less. L represents a single bond or a divalent linking group.

The compound represented by the formula (15) is preferably represented by the formula (15a-1).

Wherein X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or nitrogen atom. Any one or more of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent. X ⁵³ , X ⁵⁴ and X ⁵⁵ each independently represent a carbon or nitrogen atom, and the 5-anthracene ring skeleton containing X ⁵³ , X ⁵⁴ and X ^{55 has} a number of nitrogen atoms of 1 or 2. L represents a single bond or a divalent linking group.

The compound represented by the formula (15a-1) is preferably represented by the formula (15a-2).

In the general formula (15a-2), X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or a nitrogen atom. Any one or more of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent. X ⁵³ and X ⁵⁴ each independently represent a carbon or nitrogen atom, and the 5-membered ring skeleton containing X ⁵³ and X ^{54 has} a number of nitrogen atoms of 1 or 2. R ⁷⁵ represents a hydrogen atom or a substituent. L represents a single bond or a divalent linking group.

The compound represented by the formula (15a-2) is preferably represented by the formula (15a-3).

In the general formula (15a-3), X ¹ , X ² and X ⁴ each independently represent a carbon or a nitrogen atom. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent. X ⁵³ and X ⁵⁴ each independently represent a carbon or nitrogen atom, and the 5-membered ring skeleton containing X ⁵³ and X ^{54 has} a number of nitrogen atoms of 1 or 2. R ⁷⁵ represents a hydrogen atom or a substituent. L represents a single bond or a divalent linking group.

The compound represented by the formula (15) is preferably represented by the formula (15b-1).

In the general formula (15b-1), X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or a nitrogen atom. Any one or more of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent. X ⁶¹ is a carbon or nitrogen atom. X ¹³ , X ¹⁴ and X ¹⁵ each independently represent a carbon, nitrogen, oxygen or sulfur atom, and the number of nitrogen atoms contained in the 5-membered ring skeleton represented by X ⁶¹ , carbon atom, X ¹³ , X ¹⁴ and X ¹⁵ is 2 or less. L represents a single bond or a divalent linking group.

The compound represented by the formula (15b-1) is preferably represented by the formula (15b-2).

In the general formula (15b-2), X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or a nitrogen atom. Any one or more of X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent. X ⁹⁴ and X ⁹⁵ each independently represent a carbon or nitrogen atom, and at least one of X ⁹⁴ and X ⁹⁵ represents a carbon atom. R ⁹³ represents a hydrogen atom or a substituent. L form key or divalent link.

The compound represented by the formula (15b-2) is preferably represented by the formula (15b-3).

In the general formula (15b-3), X ¹ , X ² and X ⁴ each independently represent a carbon or a nitrogen atom. Any one or more of X ¹ , X ² and X ⁴ represents a nitrogen atom. R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent. X ⁹⁴ and X ⁹⁵ each independently represent a carbon or nitrogen atom, and at least one of X ⁹⁴ and X ⁹⁵ represents a carbon atom. R ⁹³ represents a hydrogen atom or a substituent. L represents a single bond or a divalent linking group.

Specific examples of the electron-transporting phosphorescent material which can be used in the present invention are the following compounds, but are not limited to the following compounds.

A polydentate ligand metal complex having a partial structure represented by the above formula (2) and the formulae (15), (15a-1), (15a-2), (15a-3), (15b-1) At least one of the tetradentate ligand platinum complex represented by (15b-2) and (15b-3) is contained in at least one of the organic layers, and is preferably contained in the light-emitting layer.

A polydentate ligand metal complex having a partial structure represented by the above formula (2) and the formulae (15), (15a-1), (15a-2), (15a-3), (15b-1) And at least one of the tetradentate ligand platinum complex represented by (15b-2) and (15b-3) and at least one host material is preferably contained in the light-emitting layer, and may also contain adamantane or the like. additive.

In this case, the content of the electron-transporting phosphorescent material as the luminescent dopant in the light-emitting layer is usually preferably from 0.1 to 90% by weight, more preferably from 1 to 90% by weight based on the total weight of the compound forming the light-emitting layer. 50% by weight, more preferably 1 to 25% by weight.

As the host material, any of an electron transporting body and a hole transporting body can be preferably used, and an electron transporting body and a hole transporting body can be used in combination.

<Electron transporting host material>

The electron transporting host material used in the present invention preferably has an electron affinity Ea of 2.5 eV or more and 3.5 eV or less, more preferably 2.6 eV or more and 3.4 eV or less, and more preferably 2.8 eV or more, from the viewpoint of improving durability and lowering driving voltage. Below 3.3eV. Further, from the viewpoint of improving durability and lowering the driving voltage, the free potential Ip is preferably 5.7 eV or more and 7.5 eV or less, more preferably 5.8 eV or more and 7.0 eV or less, and still more preferably 5.9 eV or more and 6.5 eV or less.

The preferred lowest triplet excitation level (hereinafter referred to as T1) is preferably 2.2 eV or more and 3.7 eV or less, more preferably 2.4 eV or more and 3.7 eV or less, and more preferably 2.4 eV or more and 3.4 eV or less.

Specific examples of the electron transporting substance include pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazole, anthrone, quinodimethane, anthrone, biphenyl fluorene, and thiophene sulphide. An aromatic cyclotetracarboxylic dianhydride, a phthalocyanine, an anthracene, a fluorinated aromatic compound, a naphthalene, an anthracene or the like, an aromatic cyclic tetracarboxylic dianhydride, a phthalocyanine, and the like a metal complex or a metal phthalocyanine of a quinolinol derivative or a metal complex which has a benzoxazole or a benzothiazole as a ligand, which forms a condensed ring with other rings) Metal complexes, etc.

The electron transporting host is preferably a metal complex, an azole derivative (benzimidazole derivative, imidazopyridine derivative, etc.), a azine derivative (pyridine derivative, pyrimidine derivative, triazine derivative, etc.), wherein In the present invention, in terms of durability, a metal complex is preferable, and more preferably a metal complex containing a ligand having at least one nitrogen, oxygen or sulfur atom coordinated to the metal.

The metal ion in the metal complex is not particularly limited, and is preferably ruthenium, magnesium, aluminum, gallium, zinc, indium, tin, platinum or palladium ions, more preferably ruthenium, aluminum, gallium, zinc, platinum or palladium ions. More preferably, it is aluminum, zinc, platinum or palladium ions.

The ligands contained in the above metal complexes may be various known ligands such as "Photochemistry and Photophysics of Coordination Compounds" (Springer-Verlag, H. Yersin, issued in 1987) and "Organic Metal Chemistry - Basics" And the application--(Shanghuafang Publishing House, Yamamoto Akio, issued in 1982) and other ligands.

Preferably, the above ligand is a nitrogen-containing heterocyclic ligand (preferably having a carbon number of 1 to 30, more preferably 2 to 20, and most preferably 3 to 15), which may be a single-dentate ligand or a double tooth. The above ligand is preferably a ligand having less than six teeth and more than six teeth. Mixed ligands for the ligands below the six teeth and the monodentate ligands above the double teeth are also preferred.

The ligand is, for example, a azine ligand (such as a pyridine ligand, a bipyridine ligand, a terpyridine ligand, etc.), a hydroxyphenylazole ligand (such as a hydroxyphenylbenzimidazole ligand, a hydroxyl group). Phenylbenzoxazole ligand, hydroxyphenylimidazole ligand, hydroxyphenylimidazolium pyridine ligand, etc.), alkoxy ligand (better 1 to 30, preferably 1 to 20, 1 ~10 is particularly good, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), aryloxy ligand (carbon number 6 ~ 30 is better, 6 ~ 20 is better, 6 ~ 12 particularly preferred, such as phenoxy, 1-naphthyloxy, 2-naphthyloxy, 2,4,6-trimethylphenoxy, 4-biphenyloxy, etc.), heteroaryloxy ligands ( Carbon number 1~30 is better, 1~20 is better, 1~12 is better, such as pyridinoxy, pyrazinyloxy, pyrimidinyloxy, quinolineoxy, etc.), alkylthio ligand (carbon number 1) ~30 is better, 1~20 is better, 1~12 is better, such as methylthio, ethylthio, etc.), aromatic sulfur coordination Base (carbon number 6~30 is better, 6~20 is better, 6~12 is better, such as phenylthio group, etc.), heteroaryl sulfide ligand (carbon number is 1~30 is better, 1~20 is better, 1~12 is particularly good, such as pyridylthio, 2-benzoimidazolium, 2-benzoxazole thiol, 2-benzothiazolylthio, etc.), decaneoxy ligand (carbon number 1~30) Good, 3~25 is better, 6~20 is better, such as triphenylnonyloxy, triethoxydecyloxy, triisopropyldecyloxy, etc.), aromatic hydrocarbon anion ligand (carbon number) 6~30 is better, 6~25 is better, 6~20 is better, such as benzene anion, naphthalene anion, anthracene anion, etc.), aromatic heterocyclic anion ligand (carbon number 1~30 is better, 2~25) More preferably, 2~20 is particularly good, such as pyrrole anion, pyrazole anion, triazole anion, oxazole anion, benzoxazole anion, thiazole anion, benzothiazole anion, thiophene anion, benzoquinone anion, etc.), false a ruthenium anion ligand, etc., preferably a nitrogen-containing heterocyclic ligand, an aryloxy ligand, a heteroaryloxy or a decaneoxy ligand, more preferably a nitrogen-containing heterocyclic ligand, an aryloxy group Site group, decaneoxy ligand, aromatic hydrocarbon anion ligand or aromatic A heterocyclic anionic ligand.

Examples of the metal complex electron transporting host material are: Japanese Patent Publication No. 2002-235076, Japanese Patent Publication No. 2004-214179, Japanese Patent Publication No. 2004-221062, Japanese Patent Publication No. 2004-221065, Japanese The compound described in JP-A-2004-221068, and JP-A-2004-327313.

Specifically, the above-mentioned electron transporting host material is, for example, the following materials, but is not limited to the following materials.

<hole transmission main body material>

From the viewpoint of improving durability and lowering the driving voltage, the hole transporting host material used in the light-emitting layer of the present invention preferably has a free potential Ip of 5.1 eV or more and 6.4 eV or less, more preferably 5.4 eV or more and 6.2 eV or less. Good 5.6eV or more and 6.0eV or less. Further, from the viewpoint of improving durability and lowering the driving voltage, the electron affinity Ea is preferably 1.2 eV or more and 3.1 eV or less, more preferably 1..4 eV or more and 3.0 eV or less, and still more preferably 1.8 eV or more and 2.8 eV or less.

The preferred lowest triplet excitation level (hereinafter referred to as T1) is preferably 2.2 eV or more and 3.7 eV or less, more preferably 2.4 eV or more and 3.7 eV or less, and more preferably 2.4 eV or more and 3.4 eV or less.

The above-mentioned hole transporting host material is, for example, pyrrole, hydrazine, carbazole, azaindole, azacarbazole, pyrazole, imidazole, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, Arylamine, amine-substituted chalcone, styryl fluorene, anthrone, anthracene, stilbene, decazane, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylene a conductive polymer oligomer such as a compound, a porphyrin compound, a polydecane compound, a poly(N-vinylcarbazole), an aniline copolymer, a thiophene oligomer or a polythiophene, an organic decane, a carbon film, or Such derivatives and the like.

Preferred among them are an anthracene derivative, a carbazole derivative, an azaindole derivative, an azacarbazole derivative, an aromatic tertiary amine compound, a thiophene derivative, and particularly preferably a plurality of ruthenium in the molecule. An anthracene skeleton, a carbazole skeleton, an azaindole skeleton, an azacarbazole skeleton or an aromatic tertiary amine skeleton.

Further, in the present invention, a host material obtained by substituting a part or all of hydrogen of a host material with ruthenium may be used (Japanese Patent Application No. 2008-126130, Japanese Patent Application Publication No. 2004-515506).

The specific compound which is the above-mentioned hole transporting host material is, for example, the following compound, but is not limited to the following compounds.

The light-emitting layer has a function of receiving a hole from an anode, a hole injection layer or a hole transport layer when receiving an electric field and receiving electrons from a cathode, an electron injection layer or an electron transport layer, and providing a recombination place of a hole and an electron. Glowing.

The light-emitting layer is not particularly limited, and can be formed by a known method. For example, it can be suitably formed by a dry film forming method such as a vapor deposition method or a sputtering method, a wet coating method, a transfer method, a printing method, an inkjet method, or the like.

The thickness of the light-emitting layer is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 2 to 500 nm, and more preferably 3 to 200 nm, and more preferably 10 to 200 nm from the viewpoint of external quantum efficiency. Further, the light-emitting layer may be one layer or two or more layers, and each layer may emit light of a different color.

The organic electroluminescent device of the present invention has an organic layer containing a light-emitting layer between the anode and the cathode, and may include other layers for the purpose.

The organic layer may include at least the light-emitting layer, and may further include an electron transport layer and an electron injection layer, and may further include a hole injection layer, a hole transport layer, a hole barrier layer, an electron blocking layer, and the like, as needed.

<Electron injection layer, electron transport layer>

The electron injecting layer and the electron transporting layer have a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side.

The electron transport layer is formed by containing a material such as the electron transport host material and the electron-accepting dopant.

The thickness of the electron injecting layer and the electron transporting layer is not particularly limited, and may be appropriately selected depending on the purpose, and is preferably 500 nm or less from the viewpoint of lowering the driving voltage.

The thickness of the electron transport layer is preferably from 1 to 500 nm, more preferably from 5 to 200 nm, still more preferably from 10 to 100 nm. Further, the thickness of the electron injecting layer is preferably from 0.1 to 200 nm, more preferably from 0.2 to 100 nm, still more preferably from 0.5 to 50 nm.

The electron injecting layer and the electron transporting layer may be a single layer structure containing one or more kinds of materials, or may be a multilayer structure including a plurality of layers having the same composition or different compositions.

<hole injection layer, hole transmission layer>

The hole injection layer and the hole transport layer have a function of receiving a hole from the anode or the anode side and transmitting it to the cathode side. The hole injection layer and the hole transport layer may be a single layer structure, or may be a multilayer structure including a plurality of layers of the same composition or different compositions.

The hole injecting material or the hole transporting material used for the film layers may be a low molecular compound or a high molecular compound.

The above-mentioned hole injecting material or hole transporting material is not particularly limited and may be appropriately selected depending on the purpose, for example, a pyrrole derivative, a carbazole derivative, a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, A polyalkane derivative, a pyrazoline derivative, a pyrazolone derivative, a phenylenediamine derivative, an arylamine derivative, an amine-substituted chalcone derivative, a styrylpurine derivative, an anthrone Derivative, anthracene derivative, stilbene derivative, decazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylene compound, phthalocyanine compound, porphyrin system a compound, a thiophene derivative, an organodecane derivative, carbon or the like. These materials may be used alone or in combination of two or more.

The hole injection layer and the hole transport layer may contain electron-withdrawing dopants.

When the above electron-withdrawing dopant has a property of oxidizing an organic compound by electron-withdrawing property, an inorganic compound or an organic compound may be used.

The above inorganic compound is not particularly limited and may be appropriately selected depending on the purpose, for example, a metal halide such as iron (III) chloride, aluminum chloride, gallium chloride, indium chloride or antimony pentachloride; vanadium pentoxide or molybdenum trioxide. Etc. metal oxides, etc.

The organic compound is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a compound having a substituent such as a nitro group, a halogen group, a cyano group or a trifluoromethyl group; an anthraquinone compound, an acid anhydride compound, and fullerene.

These electron-withdrawing dopants may be used singly or in combination of two or more.

The amount of the above electron-absorbing dopant is different depending on the type of the material, and is preferably 0.01 to 50% by weight, more preferably 0.05 to 20% by weight, and even more preferably 0.1 to 10%, with respect to the hole transport layer material or the hole injecting material. %.

The hole injection layer and the hole transport layer may be formed by a known method, and may be, for example, a dry film formation method such as a vapor deposition method or a sputtering method, a wet coating method, a transfer method, a printing method, or an inkjet method. form.

The thickness of the hole injection layer and the hole transport layer is preferably 1 to 500 nm, more preferably 5 to 200 nm, and still more preferably 10 to 100 nm.

<hole blocking layer, electron blocking layer>

The hole blocking layer has a function of preventing a hole transmitted from the anode side to the light emitting layer from passing through the cathode side, and is generally provided as an organic compound layer adjacent to the light emitting layer on the cathode side.

The above electron blocking layer has a function of preventing electrons transmitted from the cathode side to the light-emitting layer from passing through the anode side, and is usually provided as an organic compound layer adjacent to the light-emitting layer on the anode side.

The compound constituting the above-mentioned hole blocking layer is, for example, an aluminum complex such as BAlq, a triazole derivative, or a phenanthroline derivative such as BCP (bathocuproine).

As the compound constituting the above electron blocking layer, for example, a compound exemplified as the above-mentioned hole transporting material can be used.

The electron blocking layer and the hole blocking layer are not particularly limited, and may be formed by a known method. For example, a dry film forming method such as a vapor deposition method or a sputtering method, a wet coating method, a transfer method, a printing method, or a spray method may be used. The ink method or the like is appropriately formed.

The thickness of the hole blocking layer and the electron blocking layer is preferably 1 to 200 nm, more preferably 1 to 50 nm, and still more preferably 3 to 10 nm. Further, the hole blocking layer and the electron blocking layer may be a single layer structure containing one or more of the above materials, or may be a multilayer structure containing a plurality of layers of the same or different compositions.

<electrode>

The organic electroluminescent device of the present invention comprises a pair of electrodes, namely an anode and a cathode. In terms of the nature of the organic electroluminescent device, at least one of the anode and the cathode is preferably a transparent electrode. In general, the anode may have a function as an electrode for supplying a hole to the organic compound layer, and the cathode may have a function as an electrode for injecting electrons into the organic compound layer.

The shape, structure, size, and the like of the above-described electrode are not particularly limited, and can be appropriately selected from known electrode materials in accordance with the use and purpose of the organic electroluminescent device.

The material constituting the above electrode may, for example, be a metal, an alloy, a metal oxide, a conductive compound, or a mixture thereof.

-anode-

The material constituting the anode is, for example, a conductive metal oxide such as tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO) or indium zinc oxide (IZO) doped with antimony or fluorine; Metals such as gold, silver, chromium, nickel; mixtures or laminates of such metals with conductive metal oxides; inorganic conductive materials such as copper iodide and copper sulfide; polyaniline, polythiophene, polypyrrole An organic conductive material, or a laminate of such materials and ITO, or the like. Preferred among these materials are conductive metal oxides, and ITO is particularly preferable in terms of productivity, high electrical conductivity, transparency, and the like.

-cathode-

The materials constituting the cathode are, for example, alkali metals (such as Li, Na, K, Cs, etc.), alkaline earth metals (such as Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloy, lithium-aluminum alloy, magnesium- A rare earth metal such as a silver alloy, indium or bismuth. These materials may be used alone or in combination of two or more kinds in view of achieving stability and electron injectability at the same time.

Among these materials, an alkali metal or an alkaline earth metal is preferable in terms of electron injectability, and a material mainly composed of aluminum is preferable in terms of good storage stability.

The above-mentioned material mainly composed of aluminum refers to an alloy of pure aluminum, aluminum and 0.01 to 10% by weight of an alkali metal or an alkaline earth metal (for example, a lithium aluminum alloy, a magnesium aluminum alloy, etc.), or a mixture of such materials ().

The method for forming the above electrode is not particularly limited, and can be carried out by a known method, for example, a wet method such as a printing method or a coating method; a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method; and chemical vapor deposition (CVD) The chemical method such as the plasma CVD method can be appropriately selected in consideration of the suitability of the material constituting the above electrode, and the electrode can be formed on the substrate by a selected method. For example, when ITO is selected as the anode material, the electrode can be formed by direct current or high frequency sputtering, vacuum evaporation, ion plating, or the like. When a metal or the like is selected as the cathode material, one or two or more kinds thereof may be simultaneously or sequentially formed by a sputtering method or the like.

Further, when patterning is performed when the electrode is formed, it can be patterned by chemical etching using a lithography method or the like, or can be patterned by physical etching using laser or the like, and the mask can be overlapped. Patterning is performed by vacuum vapor deposition, sputtering, or the like, and patterning may be performed by a lift-off method or a printing method.

<Substrate>

The organic electroluminescent device of the present invention is preferably provided on a substrate, and may be provided in a form in which the electrodes are in direct contact with the substrate, or may be provided in the form of an intermediate layer.

The material of the substrate is not particularly limited, and may be appropriately selected depending on the purpose, for example, inorganic materials such as yttria-stabilized zirconia (YSZ), glass (alkali-free glass, soda-lime glass, etc.); polyethylene terephthalate, Polyesters such as polybutylene phthalate and polyethylene naphthalate; polystyrene, polycarbonate, polyether oxime, polyarylate, polyimine, polycycloolefin, norbornene resin, Organic materials such as poly(chlorotrifluoroethylene).

The shape, structure, size, and the like of the substrate are not particularly limited, and may be appropriately selected depending on the use, purpose, and the like of the light-emitting element. Generally, the shape of the substrate is preferably a plate shape. The structure of the substrate may be a single layer structure or a laminated structure, and may be formed of a single member or may be formed of two or more members. The substrate can be transparent or opaque. In the case where the substrate is transparent, it may be colorless and transparent, or may be colored and transparent.

Further, a moisture-proof layer (gas barrier layer) may be provided on the surface or the back surface of the substrate.

The material of the moisture-proof layer (gas barrier layer) is, for example, an inorganic material such as tantalum nitride or ruthenium oxide.

The moisture-proof layer (gas barrier layer) can be formed, for example, by a high-frequency sputtering method or the like.

-The protective layer-

The entirety of the organic electroluminescent element can be protected by a protective layer.

The material contained in the protective layer may have a function of suppressing the deterioration of the element such as moisture or oxygen, and is not particularly limited, and may be appropriately selected depending on the purpose, for example, In, Sn, Pb, Au, Cu, Ag. Metals such as Al, Ti, Ni; metal oxides such as MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, Fe ₂ O ₃ , Y ₂ O ₃ , TiO ₂ ; SiN _x , SiN Metal nitride such as _x O _y ; metal fluoride such as MgF ₂ , LiF, AlF ₃ , CaF ₂ ; polyethylene, polypropylene, polymethyl methacrylate, polyimine, polyurea, polytetrafluoroethylene, poly a copolymer of chlorotrifluoroethylene, polydichlorodifluoroethylene, chlorotrifluoroethylene and dichlorodifluoroethylene, a copolymer obtained by copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer, A fluorinated copolymer having a cyclic structure on the copolymerization main bond, a water-absorbent substance having a water absorption ratio of 1% or more, a moisture-proof substance having a water absorption ratio of 0.1% or less, or the like.

The method for forming the protective layer is not particularly limited and may be appropriately selected depending on the purpose, such as vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, and ion plating. Method, plasma polymerization method (high-frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method, and the like.

- sealed container -

The organic electroluminescent element of the present invention can be sealed entirely using a sealed container. Further, a space between the sealed container and the organic electroluminescent device may be filled with a moisture absorbent or an inert liquid.

The above moisture absorbent is not particularly limited and may be appropriately selected depending on the purpose, for example, cerium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride. , barium fluoride, barium fluoride, calcium bromide, vanadium bromide, molecular sieves, zeolites, magnesium oxide, and the like.

The inert liquid is not particularly limited and may be appropriately selected depending on the purpose, for example, paraffin wax, mobile paraffin, fluorine-based solvent such as perfluoroalkane, perfluoroamine or perfluoroether; chlorine-based solvent, silicone oil, and the like.

- resin sealing layer -

The organic electroluminescent device of the present invention is preferably sealed with a resin sealing layer to suppress deterioration of element performance due to oxygen or moisture from the atmosphere.

The resin material of the resin sealing layer is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include an acrylic resin, an epoxy resin, a fluorine resin, a polyoxyn resin, a rubber resin, and an ester resin. Among these materials, in terms of waterproof function, epoxy resin is particularly preferred. Preferred among the epoxy resins are thermosetting epoxy resins or photocurable epoxy resins.

The method for producing the resin sealing layer is not particularly limited, and may be appropriately selected depending on the purpose, for example, a method of applying a resin solution, a method of pressure bonding or thermocompression bonding a resin sheet, and dry polymerization by vapor deposition or sputtering. Method, etc.

- Sealing Adhesive -

The sealing adhesive used in the present invention has a function of preventing entry of moisture or oxygen from the end portion.

The material of the above sealing adhesive may be the same as that used for the above resin sealing layer. Among these materials, an epoxy-based adhesive is preferred for preventing moisture, and a photocurable adhesive or a thermosetting adhesive is particularly preferred.

It is also preferable to add a filler to the above sealing adhesive. The filler is preferably an inorganic material such as SiO ₂ , SiO (yttria), SiON (niobium oxynitride), or SiN (tantalum nitride). By adding a filler, the viscosity of the sealant is increased, the processability is improved, and the moisture resistance is improved.

The above sealing adhesive may contain a desiccant such as cerium oxide, calcium oxide, cerium oxide or the like. The amount of the desiccant added is preferably from 0.01 to 20% by weight, more preferably from 0.05 to 15% by weight, based on the above-mentioned sealing adhesive. If the amount added is less than 0.01% by weight, the effect of adding the desiccant is slight; if it exceeds 20% by weight, it is difficult to uniformly disperse the desiccant in the sealing adhesive.

In the present invention, the sealing adhesive to which the desiccant is added may be applied in an arbitrary amount by a dispenser or the like, and after the second substrate is superposed, it is cured to be sealed.

Fig. 1 is a schematic view showing an example of a layer structure of an organic electroluminescent device of the present invention. The layer structure of the organic EL element 10 is composed of an anode 2 (for example, an ITO electrode) formed on the glass substrate 1, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, and an electron injection layer 7, The cathode 8 (for example, an Al-Li electrode) is sequentially stacked. Further, the anode 2 (such as an ITO electrode) and the cathode 8 (such as an Al-Li electrode) are connected to each other via a power source.

-drive-

The organic electroluminescent device of the present invention can emit light by applying a direct current (which may contain an alternating current component) voltage (usually 2V to 15V) or a direct current between the anode and the cathode.

The organic electroluminescent element of the present invention can be adapted for active matrix driving by means of a thin film transistor. The active layer of the thin film transistor may be an amorphous germanium, a high temperature polycrystalline germanium, a low temperature polycrystalline germanium, a microcrystalline germanium, an oxide semiconductor, an organic semiconductor, a carbon nanotube, or the like.

The organic electroluminescent device of the present invention is, for example, a thin film transistor described in the specification of WO2005/088726, Japanese Patent Publication No. 2006-165529, and the specification of US Patent Application Publication No. 2008/0237598A1.

The organic electroluminescent device of the present invention is not particularly limited, and the light emission efficiency can be improved by various known methods. For example, by processing the surface shape of the substrate (for example, forming a fine uneven pattern), controlling the refractive index of the substrate, the ITO layer, and the organic layer, and controlling the thickness of the substrate, the ITO layer, and the organic layer, the light emission efficiency can be improved. To improve external quantum efficiency.

The method of emitting light from the organic electroluminescence element of the present invention may be a top emission method or a bottom emission method.

The organic electroluminescent device of the present invention may have a resonator structure, for example, a multilayer film mirror having a multi-layer film having different refractive indices, a transparent or semi-transparent electrode, a light-emitting layer, and a metal electrode, which are stacked on a transparent substrate. The light generated by the light-emitting layer is a multi-layered mirror and a metal electrode as a reflecting plate, and is repeatedly reflected and resonated therebetween.

Another preferred embodiment is that the transparent or semi-transparent electrode and the metal electrode respectively function as a reflecting plate on the transparent substrate, and the light generated by the light-emitting layer is reflected and reciprocated therebetween to resonate.

In order to form a resonant structure, the optical path determined by the effective refractive index of the two reflecting plates, the refractive index of each layer between the reflecting plates, and the thickness can be adjusted to an optimum value at which a desired resonant wavelength can be obtained. The equation in the case of the first type is described in Japanese Patent Laid-Open Publication No. Hei 9-180883. The equation in the case of the second type is described in Japanese Patent Laid-Open Publication No. 2004-127795.

-use-

The use of the organic electroluminescent device of the present invention is not particularly limited, and may be appropriately selected depending on the purpose, and is preferably used for a display element, a display, a backlight, an electronic photograph, an illumination source, a recording light source, an exposure light source, a reading light source, a logo, and a signboard. , interior decoration, optical communication, etc.

For example, a method of making the above-described organic EL display into a full-color display is known as an organic EL that emits light corresponding to three primary colors (blue-green-red, BGR) as described in "Monitoring Monthly", September, 2003, pages 33-37. a three-color luminescence method in which a component is disposed on a substrate, a white method in which white light emitted from a white organic light-emitting device is divided into three primary colors by a color filter, and blue light emitted from a blue organic electroluminescent device is converted into a red color through a fluorescent pigment layer. And green color conversion method. Further, a plurality of organic light-emitting elements of different luminescent colors obtained by the above methods are used in combination to obtain a planar light source of a desired luminescent color, for example, a white light source in which blue and yellow light-emitting elements are combined, and blue, green, and red are combined. A white light source made of a light-emitting element.

[Experimental example]

The experimental examples of the present invention are described below, but the present invention is not limited thereto.

(Comparative Example 1) -Production of organic electric field light-emitting elements -

A glass substrate having a thickness of 0.5 mm and a thickness of 2.5 cm was placed in a washing container, ultrasonically washed in 2-propanol, and subjected to ultraviolet-ozone treatment for 30 minutes, and the following layers were vapor-deposited thereon by vacuum evaporation. Unless otherwise specified, the vapor deposition rate in the following experimental examples and comparative examples was 0.2 nm/s. The vapor deposition rate was measured using a crystal oscillator, and the thickness of each of the following layers was also.

100 nm thick indium tin oxide was sputtered on the glass substrate as an anode.

Then, a 140 nm thick 2-TNATA (4,4',4"-tris(N-(2-naphthyl)-N-phenylamino)triphenylamine) was deposited as a hole injection on the ITO anode. Floor.

Next, 7 nm thick α-NPD (bis[N-(1-naphthyl)-N-phenyl]benzidine) was deposited as a hole transport layer on the hole injection layer.

Then, a 3 nm-thick amine compound 1 represented by the following structural formula was deposited on the hole transport layer as a second hole transport layer.

Then, a light-emitting layer of 30 nm thick is deposited on the second hole transport layer, and the light-emitting layer is doped with H-4 [mCP:(N,N'-II) represented by the following structural formula as a host material for hole transporting. Carbazolyl-3,5-benzene)], and Firpic [bis(4,6-difluorophenylpyridine-N,C2)pyridine as a hole transporting phosphorescent material with respect to the mCP of 6.0 wt%) Hyperthyroidism (III)].

Then, a nitrogen-containing heterocyclic derivative 1 represented by the following structural formula having a thickness of 40 nm was deposited on the light-emitting layer as an electron transporting layer, which is a high electron transporting material included in the general formula (1).

Then, 1 nm thick LiF was vapor-deposited on the electron transport layer as an electron injection layer.

Next, a patterned mask having a light-emitting region of 2 × 2 mm ² was provided on the electron injection layer, and metal aluminum having a thickness of 100 nm was vapor-deposited as a cathode.

The laminated body produced in the above procedure was placed in an argon-substituted glove box, and sealed with a stainless steel sealed can and an ultraviolet curable adhesive XNR5516HV (manufactured by Nagase Chiba Co., Ltd.) to prepare an organic electroluminescent device of Comparative Example 1.

(Comparative Example 2) -Production of organic electric field light-emitting elements -

In addition to using BAlq [bis(2-methyl-8-hydroxyquinoline-N1,O8)-(4-phenylphenol)aluminum (III)] as a low electron transporting material as an electron transport layer, An organic electroluminescence device was produced in the same manner as in Example 1.

(Comparative Example 3) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Comparative Example 2 except that D-1 represented by the following structural formula of the electron-transporting phosphorescent material included in the general formula (2) was used as the light-emitting material.

(Experimental Example 1) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Comparative Example 1, except that D-1 represented by the above structural formula was used instead of Firpic as a light-emitting material.

(Experimental Example 2) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 1, except that the nitrogen-containing heterocyclic derivative 2 represented by the following structural formula was used as the electron transporting layer.

(Experimental Example 3) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 1, except that the nitrogen-containing heterocyclic derivative 3 represented by the following structural formula was used as the electron transporting layer.

(Experimental Example 4) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 1, except that the nitrogen-containing heterocyclic derivative 4 represented by the following structural formula was used as the electron transporting layer.

(Experimental Example 5) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 1, except that D-2 represented by the following structural formula was used as a light-emitting material.

(Experimental Example 6) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 5 except that H-24 represented by the following structural formula was used as a host material and the nitrogen-containing heterocyclic derivative 2 represented by the above structural formula was used as an electron transport layer.

(Experimental Example 7) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 5 except that H-27 represented by the following structural formula was used as a host material and the nitrogen-containing heterocyclic derivative 3 represented by the above structural formula was used as an electron transport layer.

(Experimental Example 8) -Production of organic electric field light-emitting elements -

In addition to using H-17 represented by the following structural formula as a host material, D-3 represented by the following structural formula is used as a light-emitting material, and the nitrogen-containing heterocyclic derivative 4 represented by the above structural formula is used as an electron transport layer, In the same manner as in Experimental Example 1, an organic electroluminescent element was produced.

(Experimental Example 9) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 1, except that D-4 represented by the following structural formula was used as a light-emitting material.

(Experimental Example 10) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 9 except that H-24 represented by the above structural formula was used as a host material and the nitrogen-containing heterocyclic derivative 2 represented by the above structural formula was used as an electron transport layer.

(Experimental Example 11) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 1, except that D-5 represented by the following structural formula was used as a light-emitting material and the nitrogen-containing heterocyclic derivative 3 represented by the above structural formula was used as an electron transport layer.

(Experimental Example 12) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 1, except that D-9 represented by the following structural formula was used as a light-emitting material and the nitrogen-containing heterocyclic derivative 4 represented by the above structural formula was used as an electron transport layer.

(Experimental Example 13) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 12 except that the nitrogen-containing heterocyclic derivative 1 represented by the above structural formula was used as the electron transporting layer.

(Experimental Example 14) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 2 except that D-10 represented by the following structural formula was used as a light-emitting material.

(Experimental Example 15) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 14 except that the nitrogen-containing heterocyclic derivative 3 represented by the above structural formula was used as the electron transporting layer.

(Experimental Example 16) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 4 except that D-14 represented by the following structural formula was used as a light-emitting material.

(Experimental Example 17) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 1, except that D-15 represented by the following structural formula was used as a light-emitting material.

(Experimental Example 18) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 2 except that D-23 represented by the following structural formula was used as a light-emitting material.

(Experimental Example 19) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 3 except that D-24 represented by the following structural formula was used as a light-emitting material.

(Experimental Example 20) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 19 except that the nitrogen-containing heterocyclic derivative 4 represented by the above structural formula was used as the electron transporting layer.

Then, with respect to Experimental Examples 1 to 20 and Comparative Examples 1 to 3 produced, the driving voltage and the external quantum efficiency were measured as follows. The results are shown in Table 1.

<Measurement of driving voltage>

A power supply measuring unit 2400 manufactured by Toyo Kogyo Co., Ltd. was used to apply a direct current voltage to each element to emit light, and a voltage at a current of 10 mA/cm ² was measured as a driving voltage.

<Measurement of External Quantum Efficiency>

A DC voltage was applied to each element by the power supply measuring unit 2400 manufactured by Japan Dongyang Technology Co., Ltd. to emit light, and the luminescence spectrum and brightness were measured using a spectral analyzer SR-3 manufactured by Topcon Corporation, and then based on these values, the current was calculated by a luminance conversion algorithm. External quantum efficiency at 10 mA/cm ² .

As is clear from the results of Table 1, when Comparative Example 1 is compared with Comparative Example 2, in the case where Firpic is used as the hole-transporting phosphorescent luminescent material, the BAlq of the electron-transporting layer belonging to the low electron-transporting material is changed to be high. The nitrogen-containing heterocyclic derivative 1 of the electron transporting material has a reduced driving voltage, but the external quantum efficiency is lowered, and high quantum efficiency and low voltage generated by phosphorescence cannot be simultaneously achieved.

However, when Comparative Example 3 and Experimental Example 1 using the tetradentate ligand platinum complex (D-1) of the electron-transporting phosphorescent material were compared, the electron transport layer was changed from BAlq to a nitrogen-containing heterocyclic derivative. At 1 o'clock, a large voltage reduction can be seen, and the external quantum efficiency can be maintained at a high value. Further, from Experimental Examples 2 to 4, it was confirmed that the three kinds of nitrogen-containing heterocyclic derivatives satisfying the general formula (1) have the same effects, and it was confirmed from Experimental Examples 5 to 20 that the electron-transporting phosphorescence of the general formula (2) was satisfied. The material can still have the same effect.

(Comparative Example 4) -Production of organic electric field light-emitting elements -

In addition to changing the 2-TNATA of the hole injection layer into DNTPD (N,N'-bis[4-(di-tolylamino)phenyl]-N,N'-diphenylbiphenyl-4,4' An organic electroluminescent device was produced in the same manner as in Comparative Example 1, except that the diamine was used.

(Experimental Example 21) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Comparative Example 4 except that Firpic was changed to D-1 represented by the following structural formula as a light-emitting material.

(Experimental Example 22) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 21 except that the nitrogen-containing heterocyclic derivative 2 represented by the following structural formula was used as the electron transporting layer.

(Experimental Example 23) -Production of organic electric field light-emitting elements -

An organic electroluminescent device was produced in the same manner as in Experimental Example 21 except that the nitrogen-containing heterocyclic derivative 3 represented by the following structural formula was used as the electron transporting layer.

With respect to Comparative Example 4 and Experimental Examples 21 to 23 obtained, the driving voltage and the external quantum efficiency were measured in the same manner as in Experimental Example 1. The results are shown in Table 2.

[Industry Utilization]

The organic electroluminescent device of the present invention can achieve a low voltage of a driving voltage while maintaining high luminous efficiency, and can be preferably used, for example, for display elements, displays, backlights, electronic photographs, illumination sources, recording light sources, exposure light sources, and reading. Take light source, logo, signboard, interior decoration, light guide communication, etc.

1. . . glass substrate

2. . . anode

3. . . Hole injection layer

4. . . Hole transport layer

5. . . Luminous layer

6. . . Electronic transport layer

7. . . Electron injection layer

8. . . cathode

10. . . Organic EL element

Fig. 1 is a schematic view showing an example of a layer structure of an organic electroluminescence device of the present invention.

Claims (11)

An organic electroluminescent device comprising at least one organic layer comprising a light-emitting layer between an anode and a cathode, wherein at least one layer of the at least one organic layer contains at least one selected from the group consisting of nitrogen-containing heterocyclic derivatives represented by the formula (1) And at least one layer of the at least one organic layer contains an electron-transporting phosphorescent material represented by the formula (15a-3), Wherein, in the general formula (1), A ¹ to A ³ are each independently a nitrogen or a carbon atom; Ar ¹ is a substituted or unsubstituted core carbon number of 6 to 60 aryl groups, or a substituted or unsubstituted core carbon number of 3 to 60 Heteroaryl; Ar ² is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, a substituted or unsubstituted carbon number 1 to 20 alkane a substituted or unsubstituted C 1-20 alkoxy group; but one of Ar ¹ and Ar ² is a substituted or unsubstituted core carbon number 10 to 60 condensed ring group, or a substituted or unsubstituted core carbon number 3 to 60 monoheterofused ring groups; L ¹ and L ² are each independently a single bond, substituted or unsubstituted core carbon number 6 to 60 extended aryl group, substituted or unsubstituted core carbon number 3 to 60 heteroaryl group , or a substituted or unsubstituted hydrazine group; R is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, substituted or unsubstituted a carbon number of 1 to 20 alkyl groups, or a substituted or unsubstituted carbon number of 1 to 20 alkoxy groups; n is an integer of 0 to 5, and when n is 2 or more, a plurality of Rs may be the same or different and adjacent a plurality of R groups may be bonded to each other to form Ring aliphatic ring or an aromatic carbocyclic ring; Wherein X ¹ , X ² and X ⁴ each independently represent a carbon or nitrogen atom; R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom or a substituent; and X ⁵³ and X ⁵⁴ are each independently The carbon or nitrogen atom is represented; the number of nitrogen atoms contained in the 5-membered ring skeleton containing X ⁵³ and X ⁵⁴ is 1 or 2; R ⁷⁵ represents a hydrogen atom or a substituent; and L represents a single bond or a divalent linking group. The organic electroluminescent device according to claim 1, wherein at least one of the nitrogen-containing heterocyclic derivatives represented by the formula (1) is a nitrogen-containing heterocyclic derivative represented by the formula (3), In the general formula (3), A ¹ to A ³ are each independently a nitrogen or a carbon atom; Ar ¹ is a substituted or unsubstituted core carbon number of 6 to 60 aryl groups, or a substituted or unsubstituted core carbon number of 3 to 60 heteroaryl groups; Ar ² is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, a substituted or unsubstituted carbon number 1 to 20 alkyl group, Or a substituted or unsubstituted carbon number of 1 to 20 alkoxy; but one of Ar ¹ and Ar ² is a substituted or unsubstituted fused ring group having a core carbon number of 10 to 60, or a substituted or unsubstituted core carbon number of 3 ~60 monoheterofused ring group; L ¹ and L ² are each independently a single bond, a substituted or unsubstituted core carbon number 6 to 60 extended aryl group, a substituted or unsubstituted core carbon number of 3 to 60 heteroaryl group, Or a substituted or unsubstituted hydrazine group; R' is a hydrogen atom, a substituted or unsubstituted core carbon number 6 to 60 aryl group, a substituted or unsubstituted core carbon number 3 to 60 heteroaryl group, substituted or unsubstituted The carbon number is 1 to 20 alkyl groups, or the substituted or unsubstituted carbon number is 1 to 20 alkoxy groups. The organic electroluminescent device according to claim 2, wherein the nitrogen-containing heterocyclic derivative represented by the formula (3) is a nitrogen-containing heterocyclic derivative represented by the formula (4). Wherein, in the formula (4), A ¹ and A ² are each independently a nitrogen or a carbon atom; Ar ¹ is a substituted or unsubstituted core carbon number 6 to 60 aryl group, or a substituted or unsubstituted core carbon number 3 ~60heteroaryl; Ar ² is a hydrogen atom, substituted or unsubstituted core carbon number 6 to 60 aryl, substituted or unsubstituted core carbon number 3 to 60 heteroaryl, substituted or unsubstituted carbon number 1~ a 20 alkyl group, or a substituted or unsubstituted C 1-20 alkoxy group; but one of Ar ¹ and Ar ² is a substituted or unsubstituted core carbon number 10 to 60 condensed ring group, or a substituted or unsubstituted core a carbon number of 3 to 60 monoheterocyclic ring groups; L ¹ and L ² are each independently a single bond, a substituted or unsubstituted core carbon number of 6 to 60 aryl, a substituted or unsubstituted core carbon number of 3 to 60 An aryl group, or a substituted or unsubstituted hydrazine group; R' and R" are each independently a hydrogen atom, a substituted or unsubstituted core carbon number of 6 to 60 aryl groups, a substituted or unsubstituted core carbon number of 3 to 60 An aryl group, a substituted or unsubstituted C 1-20 alkyl group, or a substituted or unsubstituted C 1-20 alkoxy group; R' and R" may be the same or different. The organic electroluminescent device according to claim 3, wherein among the nitrogen-containing heterocyclic derivatives represented by at least one of the general formulae (1), (3) and (4), L ¹ and L ² At least one is selected from the functional groups represented by the following structural formulas, The organic electroluminescent device according to claim 3, wherein in the nitrogen-containing heterocyclic derivative represented by at least one of the general formulae (1), (3) and (4), Ar ¹ is as follows a functional group represented by any one of the formulae (5) to (14), Wherein R ¹ to R ⁹² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 1-20 alkoxy group, a substituted or unsubstituted core carbon number; 6 to 40 aryloxy, substituted or unsubstituted diarylamino group having 12 to 80 core carbon atoms, substituted or unsubstituted core carbon number 6 to 40 aryl group, substituted or unsubstituted core carbon number 3 to 40 a heteroaryl group, or a substituted or unsubstituted diarylaminoaryl group having a core carbon number of 18 to 120; L ³ represents a single bond or a substituent represented by the following structural formula, The organic electroluminescent device according to claim 1, wherein the luminescent layer comprises: a metal complex having a polydentate ligand having a partial structure represented by the general formula (2) and containing a general formula (15a-3) At least one of the platinum complexes of the tetradentate ligand represented, Wherein X ¹ , X ² , X ³ and X ⁴ each independently represent a carbon or nitrogen atom; and ¹ or more of X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom; X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each independently represent a carbon or nitrogen atom; X ¹¹ and X ¹² each independently represent a carbon or nitrogen atom, and X ¹³ , X ¹⁴ and X ¹⁵ each independently represent a carbon, nitrogen, oxygen or sulfur atom, to X. ^The number of nitrogen atoms contained in the 5-membered ring skeleton represented by X ¹² , X ¹³ , X ¹⁴ and X ¹⁵ is 2 or less; L represents a single bond or a divalent linking group. The organic electroluminescent device according to claim 6, wherein the luminescent layer contains: a multidental having a partial structure represented by the general formula (2) At least one of a ligand metal complex and a tetradentate ligand platinum complex represented by the formula (15a-3), and at least one host material. The organic electroluminescent device of claim 7, wherein the at least one host material has hole transport properties. The organic electroluminescent device according to claim 1, wherein the nitrogen-containing heterocyclic derivative is used as at least one of an electron injecting material and an electron transporting material. The organic electroluminescent device according to claim 1, wherein the layer containing the nitrogen-containing heterocyclic derivative contains a reducing dopant. The organic electroluminescent device according to claim 10, wherein the reducing dopant is selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, At least one of an alkaline earth metal halide, a rare earth metal oxide, a rare earth metal halide, an alkali metal organic complex, an alkaline earth metal organic complex, and an organic complex of a rare earth metal.